Supramolecular systems based on 1-alkyl-4-aza-1-azoniabicyclo[2.2.2]octane bromides

The aggregation in aqueous solutions of alkylated 1,4-diazabicyclo[2.2.2]octanes of various hydrophobicity and their adsorption at the water-air interface were studied by tensiometry, conductometry, potentiometry, viscosimetry, and ESR spectroscopy. The parameters of adsorption, critical micelle concentrations, concentrations of free counterions (bromide ions), and degree of binding of the counterions with micelles were determined. The intensification of the micelle formation ability of the surfactants with an elongation of the alkyl fragment was shown. The effective radii of ensembles of the hexadecyl and octadecyl derivatives were determined by the dynamic light scattering method. A relationship between the concentration dependences of the size of micelles and their shape was established.     

Spontaneous self-assembly process for threadlike micelles

More than 100 micros dissipative particle dynamics simulations were carried out to investigate the spontaneous formation process of threadlike micelles from the random configuration for surfactant molecules. Stable spherical micelles were formed during the earlier stage. These spherical micelles fused to each other and grew into rodlike and threadlike micelles during the later stage. The length and radius of a micelle were estimated by tracing the backbone positions and the distance between the head group particles and the backbone of the micelles, respectively. The ratio of the largest to the smallest principal moments of inertia for each micelle was calculated as the micelle shape.     

Micellization of AOT in aqueous sodium chloride, sodium acetate, sodium propionate, and sodium butyrate media: a case of two different concentration regions of counterion binding

Critical micelle concentrations of AOT in water in the presence of sodium chloride, sodium acetate, sodium propionate, and sodium butyrate were determined at 25 degrees C by the surface tension method. The co-ions do not have any effect on the value of critical micelle concentration. The surface density of AOT at the air-water interface increases in the presence of added electrolyte and attains a maximum value of 2.5+/-0.1 mol m-2 at a particular electrolyte concentration which is different for sodium chloride and the other three electrolytes. From the Corrin-Harkins plot it has been found that for AOT micelles the counterion binding constant has values 0.40 and 0.82 below and above approximately 0.015 mol kg-1 electrolyte concentration (c*), respectively. Measurement of sodium ion activity from the EMF method has confirmed such a shift in the counterion binding constant of AOT at c*. The higher value of the counterion binding constant for AOT has been reported for the first time. From fluorescence spectroscopy it has been found that the aggregation number of AOT is 22 in water and its average aggregation numbers in the presence of electrolytes are about 34 and 136 below and above c*, respectively. The increase by a factor of 2 in the counterion binding constant is shown to be due to a change in the shape of the AOT micelles around c*. The shape of AOT micelles in the electrolyte concentration range c* is inferred to be oblate spheroid and a change from this shape appears to occur above c*. A sudden increase in the polarity of the micelle-solution interface is also observed above c*.     

Structure and interactions in micellar solutions: molecular simulations of pluronic L64 aqueous solutions

Coarse-grained, implicit solvent molecular simulations have been conducted to investigate the structure and interactions of L64 Pluronic micelles in aqueous solutions. Simulations of an L64 solution beginning with monodisperse micelles (aggregation number Nagg = 40 chains) resulted in a narrow Gaussian distribution of Nagg centered around 40. While not fully equilibrated, this distribution supports the supposition that L64 micelles with Nagg = 40 are representative of the conditions considered and model employed. Detailed analysis of intramicellar monomers distribution and micelle shapes revealed that L64 micelles have a scalene ellipsoidal shape. Additional simulations of solutions containing 125 micelles constrained to have Nagg = 40 at polymer volume fractions of 0.024 and 0.110 were performed to study micelle-micelle structure factor, single micelle form factor, and total scattering intensity. The ability of various models utilized in analysis of scattering profiles in micellar solutions to describe the structure of the model L64 solutions was investigated. Investigation of the potential of mean force between two micelles reveals that the interactions between micelles are repulsive but on a length scale smaller than the mean micelle diameter, indicating that the micellar shape fluctuations are important in determining intermicellar interactions.     

Self-consistent field modeling of linear nonionic micelles

A self-consistent field theory is used to predict structural, mechanical, and thermodynamical properties of linear micelles of selected nonionic surfactants of the type C(n)()E(m). Upon increase in surfactant concentration the sudden micelle shape transition from spherical to cylindrical (second critical micelle concentration (cmc)) is analyzed. The cylindrical micelles consist of a body (with radius R(c) and length L) and two slightly swollen endcaps. For small L, the shape resembles a dumbbell. With increase in the length of the body, an oscillatory behavior in the grand potential of the micelle is found. The wavelength of the oscillation (lambda(d)) is proportional to the surfactant tail length n. The amplitude of these oscillations decreases exponentially with a decay length xi. In the limit of very long micelles, the grand potential converges to the endcap (free) energy E(c). This endcap energy increases approximately quadratic with the tail length and diminishes by increasing the headgroup size m. The micelle size distribution is generated showing non-monotonic features due to the presence of short dumbbells and becomes exponential when L > 8R(c). It is also shown that the endcap energy can be estimated in first order by the grand potential of the spherical micelle that coexists with infinitely long cylindrical micelles. The persistence length l(p) of these linear micelles is evaluated to estimate the relative importance of conformational entropy for these micelles.     

Effect of Increasing Concentration of Each of Three Polar Solvents (1,4-Dioxane, Dimethyl Sulfoxide, N,N-Dimethylformamide) on Changes in the Shape of Polysorbate 20 Micelles

The effect of increasing concentration of each of three polar solvents [0–40 % (v/v) 1,4-dioxane, 0–40 % (v/v) dimethyl sulfoxide (DMSO), and 0–60 % (v/v) N,N-dimethylformamide (DMF)] on changes in the shape of the surfactant polysorbate 20 (Tween 20) micelles in the aqueous, polar solvent, sodium phosphate buffer solutions (pH = 7.2, ionic strength 2.44 mmol·L^?1) were investigated by using small-angle X-ray scattering. The effect of increasing concentration of 1,4-dioxane is that the micelle shape changed from core–shell cylindrical micelles to core–shell disc micelles between concentrations of 10 and 20 % (v/v) 1,4-dioxane, and then from core–shell disc micelles to core–shell elliptic disc micelles between concentrations of 30 and 40 % (v/v) 1,4-dioxane. The effect of increasing concentration of DMSO is that the micelles changed from core–shell cylindrical micelles to core–shell disc micelles between concentrations of 0 and 10 % (v/v) DMSO. The effect of increasing concentration of DMF is that it changed the core–shell cylindrical micelles to core–shell disc micelles between concentrations of 30 and 40 % (v/v) DMF. The common effect is that the solvents shortened the height of the micelle, that is, they squashed the micelle. Moreover, the specific effect of 1,4-dioxane is that this solvent squashed and squeezed the micelle.     

光散射法研究氧化胺胶束与聚苯乙烯磺酸钠的相互作用

采用光散射法研究了十二烷基二甲基氧化胺(DDAO)胶束与聚苯乙烯磺酸钠(NaPSS)的相互作用,浊度滴定和激光光散射结果表明,DDAO胶束与NaPSS的相互作用受介质离子强度影响,但与胶束浓度无关,浊度滴定曲线出现一个转折点(β_c),而平均流体力学半径R_h对胶束离解度β的关系曲线出现2个转折点,在第一个转折点(β₁)时,胶束与NaPSS开始缔合,在第二个转折点(β₂)时,胶束与NaPSS的缔合达到饱和,β₂相当于浊度滴定曲线的转折β_c,β₂,和β₁不随离子强度而变化,采用β₁和β_c分别计算胶束与NaPSS发生缔合时的临界表面电荷密度,两者差距约为15％,电泳光散射也证实了β₁的存在.     

Structure and dynamics of concentrated micellar solutions of sodium dodecyl sulfate

In micellar solutions of sodium dodecyl sulfate, as the concentration of surfactants increases, the spheroid shape of the micelles changes from almost spherical to ellipsoidal with increasing ratio of half-axes ratio, and further the transition to cylindrical micelles occurs. The micelles in an aqueous solution can directly contact (compact aggregates) or be separated from one another by layers of intermicellar medium (periodical colloid structures). In the latter case, the thickness of the layer can significantly exceed the micelle size, and then no mutual correlation in micelle arrangement is observed. According to the data of small-angle X-ray scattering, the relationship between the surfactant concentration and formation of “quasi-crystalline” micellar structure is nonlinear, which can be due to both micelle aggregation processes and nonuniformity of their structure. The possible influence of ordered micellar structures on the diffusion mobility of micelles is shown.     

Deformation of copolymer micelles induced by amphiphilic dimer particles

Combining self-consistent-field theory and density-functional theory,we systematically study the deformation of copolymer micelles induced by the presence of amphiphilic dimer particles.Due to the amphiphilic nature,dimer particles tend to accumulate onto the interface of the copolymer micelle.With increasing concentration of the symmetric dimer particles,which are made of two identical spherical particles,the micelle deforms from the initial sphere to ellipse,dumbbell, and finally separates into two micelles.Furthermore,asymmetric dimer particles,composed by two particles with different sizes,are considered to investigate the influence of geometry of dimer particles on the deformation of the micelle.It is found that the micelle inclines to deform into dumbbell due to the additional curvature originating in the gathering of asymmetric dimer particles onto the interface of the micelle.The present study on the deformation of micelles is useful to understand the possible shape variation in the course of cell division/fusion.     

Ion decontamination with a mixture of cationic and anionic surfactants

The composition of mixed micelles and mixed micelle — solution interfaces changes with the concentration and molar ratio of the cationic and anionic surfactants present. The micelle — solution interface includes besides the headgroups of both surfactants, the counterions of the surfactant in excess. The finding of an enhanced binding of counterions to mixed micelles may be of some practical importance in decontamination.     

Micellar shape transition under dilute salt-free conditions: promotion and self-fluorescence monitoring of stimuli-responsive viscoelasticity by 1- and 2-naphthols

Effect of 1 and 2-naphthols on the shape transition of cetyl trimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPB) micelles are studied. Stimuli-responsive viscoelastic gels of long wormlike micelles are formed at low surfactant concentrations in the presence of neutral naphthols, where H-bonding plays a key role in micellar shape transition in the absence of any charge screening. Micelle-embedded naphthols also act as novel self-fluorescence probes for monitoring viscoelasticity of the system as a function of applied shear. 1H NMR study shows that the solubilization sites of naphthols in the micelle are located near the surface. While UV absorption and Fourier transform infrared studies confirm the presence of intermolecular H-bonds in micelle embedded naphthols, transmission electron micrographs of vacuum-dried samples at room temperature demonstrate the transition in shape from sphere to rodlike micelles.     

Micelles of imidazolium-functionalized polystyrene diblock copolymers investigated with neutron and light scattering

We synthesize a series of block copolymers comprising a polystyrene (PS) block and an imidazolium-functionalized PS (IL) block and characterize their assembly properties. We use small-angle neutron scattering and dynamic light scattering to determine the micelle size and shape in dilute solutions and to assess the micelle interactions in concentrated solutions. By studying a series of copolymers with fixed PS block length, we find that the length of the IL block governs the micelle dimensions. Our data suggest that these copolymers form elongated micelle structures where the IL block is extended in the micelle core. We find that these micelles can sequester water and that interactions between the micelles lead to structure factor peaks at elevated concentrations.     

Mixed micelles formed by SDS and a bolaamphiphile with carbohydrate headgroups

The formation of micelles in aqueous mixtures of a carbohydrate-based bolaamphiphile and sodium dodecyl sulfate (SDS) is investigated by surface tension and small-angle neutron scattering. The obtained values of critical micelle concentration (CMC) are analyzed within the framework of regular solution theory. Synergetic interactions between the bolaamphiphile and SDS are observed (parameter beta is negative; a minimum in the plot CMC vs composition). SANS data are collected for mixtures containing protonated and deuterated SDS. This gives us the possibility to conclude that mixed micelles with a homogeneous distribution of surfactant molecules within the micelle are formed. The shape of the micelles is found to be slightly oblate.     

孔雀绿与CTAB胶束的相互作用

以CTAB胶束模拟生命体系,用UV-Vis和荧光光谱等技术研究了孔雀绿与CTAB胶束的相互作用.结果表明,孔雀绿自发地定位于CTAB胶束栅栏层,使得胶束聚集数增加,胶束的微环境极性I1/I3下降.孔雀绿与CTAB胶束之间的结合常数K和孔雀绿在胶束相与水连续相之间的分配系数KD均随孔雀绿浓度增加而降低,表明孔雀绿与CTAB胶束之间的相互作用随孔雀绿浓度增加而降低.     

Study of valsartan interaction with micelles as a model system for biomembranes

In this study, the interaction of valsartan (VAL), an angiotensin II receptor antagonist, with cationic surfactant cetyltrimethylammonium bromide (CTAB) was investigated. The effect of cationic micelles on spectroscopic and acid-base properties of VAL was carried out using UV spectrophotometry at physiological conditions (pH 7.4). The binding of VAL to CTAB micelles implied a shift in drug acidity constant (pK(a)(water)-pK(a)(micelle)=1.69) proving the great affinity of VAL dianion for the positively charged CTAB micelle surface. To quantify the degree of VAL/CTAB interaction, two constants were calculated by using mathematical models: micelle/water partition coefficient (K(x)) and drug/micelle binding constant (K(b)). The decrease of K(x) with VAL concentration, obtained by using pseudo-phase model, is consistent with an adsorption-like phenomenon. From the dependence of differential absorbance at lambda=295 nm on CTAB concentration, by using mathematical model that treats the solubilization of VAL dianion as its binding to specific sites in the micelles (Langmuir adsorption isotherm), the binding constant (K(b)=(2.50+/-0.49)x10(4)M(-1)) was obtained. Binding constant VAL/CTAB was also calculated using micellar liquid chromatography (MLC).     

Long-chain alkyl sulfonate micelle fission: a molecular dynamics study

In this study, we investigate micelle fission of long-chain alkyl sulfonate molecules using atomistic scale simulation. GROMACS software code with the united atom force field was applied. 0.5-μs parallel molecular dynamics simulation study was conducted for a surfactant/water system consisting of 192 sodium pentadecyl sulfonate and 40,553 water molecules. The large preassembled micelle was ruptured at Krafft above T?=?323-K temperature, and we track two ellipsoid-like micelles over the course of the production run. To estimate the micelle shape, we determined the principal moments of inertia and the eccentricity, which proved that the micelles have a pronounced prolate spheroid shape, which agrees well with our previous experimental data. The mechanism of micelle fission was explored in detail. The aggregation number, ionization degree, and other parameters obtained from simulation were consistent with existing experimental finding. The determined parameters in addition to simple visual inspection of trajectories revealed monomer-micelle exchange—with the estimated relaxation time τ ₁?=?10^??9s. We assume that the exchange process is conditioned by the unequal size of micelles leading to adjustment of aggregation number.     

The Correlation of the Degree of Counterion Binding with the Composition of Ionic–Nonionic Mixed Micelles

Two simple expressions for calculating the degree of counterion binding of mixed micelles are presented. These approximate expressions for the spherical micelle are derived from the relationship of the degree of counterion binding with the surface charge density. One of them works quite well for the estimation of the degree of counterion binding of mixed micelles when the mole fraction of the ionic component in mixed micelles is high.     

Sphere-to-rod transition of non-surface-active amphiphilic diblock copolymer micelles: a small-angle neutron scattering study

Micellization behavior of amphiphilic diblock copolymers with strong acid groups, poly(hydrogenated isoprene)-block-poly(styrenesulfonate), was investigated by small-angle neutron scattering (SANS). We have reported previously (Kaewsaiha, P.; Matsumoto, K.; Matsuoka, H. Langmuir 2005, 21, 9938) that this strongly ionic amphiphilic diblock copolymer shows almost no surface activity but forms micelles in water. In this study, the size, shape, and internal structures of the micelles formed by these unique copolymers in aqueous solution were duly investigated. The SANS data were well described by the theoretical form factor of a core-shell model and the Pedersen core-corona model. The micellar shape strongly depends on the hydrophobic chain length of the block copolymer. The polymer with the shortest hydrophobic chain was suggested to form spherical micelles, whereas the scattering curves of the longer hydrophobic chain polymers showed a q-1 dependence, reflecting the formation of rodlike micelles. Furthermore, the addition of salt at high concentration also induced the sphere-to-rod transition in micellar shape as a result of the shielding effect of electrostatic repulsion. The corona thickness was almost constant up to the critical salt concentration (around 0.2 M) and then decreased with further increases in salt concentration, which is in qualitatively agreement with existing theories. The spherical/rodlike micelle ratio was also constant up to the critical salt concentration and then decreased. The micelle size and shape of this unique polymer could be described by the common concept of the packing parameter, but the anomalously stable nature of the micelle (up to 1 M NaCl) is a special characteristic.     

The sphere-rod transition of micelles of dodecyldimethylammonium bromide in aqueous NaBr solutions,and the effects of counterion binding on the micelle size,shape and structure

Micelle size and shape of dodecyldimethylammonium bromide have been determined by measurement of light scattering from its aqueous NaBr solutions. In water and in the presence of NaBr up to 0.07 M, the Debye plots give straight lines with positive slopes, and spherical micelles having molecular weight less than 30 000 are formed. At higher NaBr concentrations, the Debye plots decrease with increasing micelle concentration, indicating the aggregation of the primary spherical micelles into larger secondary micelles. The molecular weight and the radius of gyration of the secondary micelles increase with increasing NaBr concentration, and the relation between molecular weight and radius of gyration suggests that they are rodlike and flexible. Linear logarithmic relations between micelle molecular weight and ionic strength hold for spherical and rodlike micelles, respectively, and the threshold concentration of NaBr for the sphere-rod transition is located at 0.07 M. The spherical micelle of dodecyldimethylammonium ions has a size more than 20 surfactant ions larger in NaBr solutions than in NaCl solutions, and their rodlike micelle has a shorter length in NaBr solutions than in NaCl solutions, when compared at an identical aggregation number, indicating 2 more surfactant ions in its cross-section.